EP0339417B1 - 3-cyano-4-phenyl-pyrroles - Google Patents

3-cyano-4-phenyl-pyrroles Download PDF

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EP0339417B1
EP0339417B1 EP89106817A EP89106817A EP0339417B1 EP 0339417 B1 EP0339417 B1 EP 0339417B1 EP 89106817 A EP89106817 A EP 89106817A EP 89106817 A EP89106817 A EP 89106817A EP 0339417 B1 EP0339417 B1 EP 0339417B1
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Prior art keywords
cyano
formula
phenyl
pyrroles
species
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German (de)
French (fr)
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EP0339417A1 (en
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Detlef Dr. Wollweber
Wilhelm Dr. Brandes
Stefan Dr. Dutzmann
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Bayer AG
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Bayer AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/337—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms

Definitions

  • the invention relates to new 3-cyano-4-phenyl-pyrroles, a process for their preparation and their use in pesticides.
  • 3-cyano-4-phenyl-pyrroles such as the compound 3-cyano-4- (2,3-di-chlorophenyl) pyrrole or the compound 1-acetyl-3-cyano-4- (2,3-dichlorophenyl) pyrrole, have fungicidal activity (see, for example, EP 236272; DE-OS 2927480).
  • 3-cyano-4-phenyl-pyrroles such as the compound N-methoxymethylcarbonyl-3-cyano-4 (2,3-dichlorophenyl) pyrrole, which have a fungicidal activity (cf. Jp. Kokai Tokkyo Koho 8179, 672) or N- [1- (methoxyacetyloxy) -2,2,2-trichloroethyl] -3- (2,3-dichlorophenyl) -4-cyano-pyrrole, for example with a fungicidal action (cf. EP 130149).
  • New processes for the production of 4-phenylpyrrole derivatives are also known (cf. EP 174910).
  • the 3-cyano-4-phenyl-pyrroles of the general formula (I) according to the invention show i.a. a considerably better fungicidal activity than the 3-cyano-4-phenyl-pyrroles known from the prior art, such as, for example, the 3-cyano-4- (2,3-dichlorophenyl) pyrrole, which are chemically and functionally obvious compounds.
  • Formula (II) provides a general definition of the 1H-3-cyano-4-phenyl-pyrroles required as starting materials for carrying out the process according to the invention.
  • Ar preferably represents those Residues which have already been mentioned as preferred for this substituent in connection with the description of the substances of the formula (I) according to the invention.
  • Fluoranilines of the formula (IV) are known in some cases (cf., for example, J. org. Chem. 39 , 1758-1761 [1974]: J. med. Chem. 12 , 195-196 [1969] or US Pat. No. 3,900,519).
  • the sulfonyl methyl isocyanides of the formula (IX) which are also required as precursors for the preparation of the new starting materials of the formula (II) are also known (cf., for example, Synthesis 1985 , 400-402; Org. Syntheses 57 , 102-106 [1977]; J. org. Chem. 42 , 1153-1159 [1977]; Tetrahedron Lett. 1972 , 2367-2368).
  • the acylating agents of the formula (III) are generally known compounds of organic chemistry.
  • 1H-3-cyano-4-phenyl-pyrroles of the formula (II) are also obtained if ⁇ -cyanocinnamic acid esters are reacted with p-toluenesulfonylmethyl isocyanide in the presence of bases and in the presence of copper (II) salts ( see J6-1030-571 or J6-1200-984) or if one ⁇ -Substituted cinnamic acid nitriles cyclized in the presence of sodium hydride with isocyanoacetic acid esters, the pyrrole-2-carboxylic acid esters thus obtained are saponified with bases and then thermally decarboxylated (see JP 59/212468) or if phenacylamine derivatives are reacted with suitably substituted acrylonitrile derivatives (see EP 174910) or if 3-cyano-4-phenyl- ⁇ 2-pyrroline is oxidized in the presence of copper (II) salts or iron
  • EP 183217 or if ⁇ -cyanoacrylic acid derivatives are reacted with isocyanoacetic acid esters in the presence of a base and the ⁇ 2-pyrroline-2-carboxylic acid derivatives obtainable in this way are oxidatively decarboxylated in a second stage in the presence of a base and in the presence of a metal salt catalyst (cf. German Patent Application P 3718375 from June 2, 1987).
  • Inert organic solvents are suitable as diluents for carrying out the process according to the invention.
  • These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, ketones such as acetone or butanone, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as ethyl acetate or sulfoxides
  • the process according to the invention is preferably carried out in the presence of a suitable reaction auxiliary.
  • All conventional inorganic or organic bases are suitable as such. These include, for example, alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate, and also tertiary amines, such as triethylamine, N, N-dimethylaniline, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclooctane (DABCO), diazabicyclooctane (DABCO) ) or diazabicycloundecene (DBU).
  • alkali metal hydroxides such as sodium hydroxide or potassium hydroxide
  • alkali metal carbonates such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate
  • tertiary amines such as triethylamine
  • reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between -20 ° C and 150 ° C, preferably at temperatures between 0 ° C and 80 ° C.
  • 1.0 to 5.0 mol, preferably 1.0 to 1.5 mol, of acylating agent of the formula (III) and, if appropriate, 1.0 to 5.0, are generally employed per mol of 1H-3-cyano-4-phenylpyrrole of the formula (II) Mol, preferably 1.0 to 1.5 mol of reaction aids.
  • reaction products are worked up, worked up and isolated using generally customary methods (cf. also the preparation examples).
  • the active compounds according to the invention have a strong action against pests and can be used practically to combat undesirable harmful organisms will.
  • the active ingredients are suitable, for example, for use as crop protection agents, in particular as fungicides.
  • Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
  • Pythium species such as, for example, Pythium ultimum
  • Phytophthora species such as, for example, Phytophthora infestans
  • Pseudoperonospora species such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis
  • Plasmopara species such as, for example, Plasmopara viticola
  • Peronospora species such as, for example, Peronospora pisi or P.
  • Erysiphe species such as, for example, Erysiphe graminis
  • Sphaerotheca species such as, for example, Sphaerotheca fuliginea
  • Podosphaera species such as, for example, Podosphaera leucotricha
  • Venturia species such as, for example, Venturia inaequalis
  • Pyrenophora species such as, for example, Pyrenophora teres or P.
  • Drechslera graminea
  • Cochliobolus species such as, for example, Cochliobolus sativus
  • Uromyces species such as, for example, Uromyces appendiculatus
  • Puccinia species such as, for example, Puccinia recondita
  • Tilletia species such as, for example, Tilletia caries
  • Ustilago species such as, for example, Ustilago nuda or Ustilago avenae
  • Pellicularia species such as, for example, Pellicularia sasakii
  • Pyricularia species such as, for example, Pyricularia oryzae
  • Fusarium species such as, for example, Fusarium culmorum
  • Botrytis species such as, for example, Botrytis cinerea
  • Septoria species such as
  • the active compounds according to the invention can be used with particularly good success for combating diseases in fruit and vegetable cultivation, such as, for example, against the pathogen of gray bean mold (Botrytis cinerea), or for combating rice diseases, for example against the pathogen of rice stain disease (Pyricularia oryzae) or to combat cereal diseases, such as against the pathogen causing brown fur in the wheat (Leptosphaeria nodorum) or against the pathogen causing cereal snow mold (Fusarium nivale).
  • the active compounds according to the invention have good fungicidal activity in vitro.
  • the active ingredients can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV Cold and warm fog formulations.
  • formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, under pressure standing liquefied gases and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
  • extenders that is to say liquid solvents
  • surface-active agents ie emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • liquid solvents aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water;
  • Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide;
  • Solid carrier materials are suitable: for example natural rock powders such as
  • Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and in mixtures with fertilizers and growth regulators.
  • the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.
  • the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.
  • active compound 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
  • active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.
  • reaction mixture is allowed to come to room temperature, water is added, the mixture is extracted several times with ethyl acetate, the combined ethyl acetate phases are washed with water, dried over sodium sulfate and concentrated in vacuo. The residue is purified by chromatography on silica gel (mobile phase: cyclohexane / ethyl acetate 5: 1).
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
  • the compounds according to the preparation examples: 1 and 3 show a clear superiority in effectiveness compared to the prior art.
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
  • the plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80%.
  • Evaluation is carried out 7 days after the inoculation.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyrrole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Description

Die Erfindung betrifft neue 3-Cyano-4-phenyl-pyrrole, ein Verfahren zu ihrer Herstellung und ihre Verwendung in Schädlingsbekämpfungsmitteln.The invention relates to new 3-cyano-4-phenyl-pyrroles, a process for their preparation and their use in pesticides.

Es ist bekannt, daß bestimmte 3-Cyano-4-phenyl-pyrrole,wie beispielsweise die Verbindung 3-Cyano-4-(2,3-di-chlorphenyl)-pyrrol oder die Verbindung 1-Acetyl-3-cyano-4-(2,3-dichlorphenyl)-pyrrol, fungizide Wirksamkeit besitzen (vgl. z.B. EP 236272; DE-OS 2927480).It is known that certain 3-cyano-4-phenyl-pyrroles, such as the compound 3-cyano-4- (2,3-di-chlorophenyl) pyrrole or the compound 1-acetyl-3-cyano-4- (2,3-dichlorophenyl) pyrrole, have fungicidal activity (see, for example, EP 236272; DE-OS 2927480).

Weiterhin sind 3-Cyano-4-phenyl-pyrrole, wie beispielsweise die Verbindung N-Methoxymethylcarbonyl-3-cyano-4(2,3-dichlorphenyl)-pyrrol, bekannt, die eine fungizide Wirksamkeit besitzen (vgl. Jp. Kokai Tokkyo Koho 8179, 672) oder N-[1-(Methoxyacetyloxy)-2,2,2-trichlorethyl]-3-(2,3-dichlorphenyl)-4-cyano-pyrrol zum Beispiel mit fungizider Wirkung (vgl. EP 130149). Auch sind neue Verfahren zur Herstellung von 4-Phenyl-pyrrol-Derivaten bekannt (vgl. EP 174910).Furthermore, 3-cyano-4-phenyl-pyrroles, such as the compound N-methoxymethylcarbonyl-3-cyano-4 (2,3-dichlorophenyl) pyrrole, are known which have a fungicidal activity (cf. Jp. Kokai Tokkyo Koho 8179, 672) or N- [1- (methoxyacetyloxy) -2,2,2-trichloroethyl] -3- (2,3-dichlorophenyl) -4-cyano-pyrrole, for example with a fungicidal action (cf. EP 130149). New processes for the production of 4-phenylpyrrole derivatives are also known (cf. EP 174910).

Die Wirksamkeit dieser vorbekannten Verbindungen ist jedoch insbesondere bei niedrigen Aufwandmengen und Konzentrationen nicht in allen Anwendungsgebieten völlig zufriedenstellend.However, the effectiveness of these previously known compounds is not entirely satisfactory in all areas of application, in particular at low application rates and concentrations.

Es wurden neue 3-Cyano-4-phenyl-pyrrole der allgemeinen Formel (I),

Figure imgb0001

in welcher

R¹
für Chlor steht und
R²
für jeweils geradkettiges oder verzweigtes Alkyl, Alkoxy oder Alkoxyalkyl mit jeweils 1 bis 6 Kohlenstoffatomen in den einzelnen Alkylteilen steht,


gefunden.There were new 3-cyano-4-phenyl-pyrroles of the general formula (I),
Figure imgb0001
in which
R¹
stands for chlorine and
R²
represents straight-chain or branched alkyl, alkoxy or alkoxyalkyl each having 1 to 6 carbon atoms in the individual alkyl parts,


found.

Weiterhin wurde gefunden, daß man die neuen 3-Cyano-4-phenyl-pyrrole der allgemeinen Formel (I),

Figure imgb0002

in welcher

R¹
für Chlor steht und
R²
für jeweils geradkettiges oder verzweigtes Alkyl, Alkoxy oder Alkoxyalkyl mit jeweils 1 bis 6 Kohlenstoffatomen in den einzelnen Alkylteilen steht,


erhält, wenn man 1H-3-Cyano-4-phenyl-pyrrole der Formel (II),
Figure imgb0003
in welcher
R¹
die oben angegebene Bedeutung hat,


mit Acylierungsmitteln der Formel (III),
Figure imgb0004
in welcher
R²
die oben angegebene Bedeutung hat und
E
für eine elektronenanziehende Abgangsgruppe steht, gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Reaktionshilfsmittels umsetzt.

It was also found that the new 3-cyano-4-phenyl-pyrroles of the general formula (I)
Figure imgb0002
in which
R¹
stands for chlorine and
R²
represents straight-chain or branched alkyl, alkoxy or alkoxyalkyl each having 1 to 6 carbon atoms in the individual alkyl parts,


obtained if 1H-3-cyano-4-phenyl-pyrroles of the formula (II),
Figure imgb0003
in which
R¹
has the meaning given above,


with acylating agents of the formula (III),
Figure imgb0004
in which
R²
has the meaning given above and
E
represents an electron-withdrawing leaving group, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.

Schließlich wurde gefunden, daß die neuen 3-Cyano-4-phenyl-pyrrole der allgemeinen Formel (I) eine gute Wirkung gegen Schädlinge besitzen.Finally, it was found that the new 3-cyano-4-phenyl-pyrroles of the general formula (I) have a good action against pests.

Überraschenderweise zeigen die erfindungsgemäßen 3-Cyano-4-phenyl-pyrrole der allgemeinen Formel (I) u.a. eine erheblich bessere fungizide Wirksamkeit als die aus dem Stand der Technik bekannten 3-Cyano-4-phenyl-pyrrole, wie beispielsweise das 3-Cyano-4-(2,3-dichlorphenyl)-pyrrol, welche chemisch und wirkungsmäßig naheliegende Verbindungen sind.Surprisingly, the 3-cyano-4-phenyl-pyrroles of the general formula (I) according to the invention show i.a. a considerably better fungicidal activity than the 3-cyano-4-phenyl-pyrroles known from the prior art, such as, for example, the 3-cyano-4- (2,3-dichlorophenyl) pyrrole, which are chemically and functionally obvious compounds.

Die erfindungsgemäßen 3-Cyano-4-phenyl-pyrrole sind durch die Formel (I) allgemein definiert. Bevorzugt sind Verbindungen der Formel (I), bei welchen

R¹
für Chlor steht und
R²
für jeweils geradkettiges oder verzweigtes Alkyl, Alkoxy oder Alkoxyalkyl mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylteilen steht.

The 3-cyano-4-phenyl-pyrroles according to the invention are generally defined by the formula (I). Compounds of the formula (I) in which
R¹
stands for chlorine and
R²
represents straight-chain or branched alkyl, alkoxy or alkoxyalkyl each having 1 to 4 carbon atoms in the individual alkyl parts.

Ganz besonders bevorzugt sind Verbindungen der Formel (I), bei welchen

R¹
für Chlor steht und
R²
für Methyl, Ethyl, Methoxy, Ethoxy, Methoxymethyl oder Ethoxymethyl steht.

Compounds of the formula (I) in which
R¹
stands for chlorine and
R²
represents methyl, ethyl, methoxy, ethoxy, methoxymethyl or ethoxymethyl.

Im einzelnen seien außer den bei den Herstellungsbeispielen genannten Verbindungen die folgenden 3-Cyano-4-phenyl-pyrrole der allgemeinen Formel (I) genannt:

Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
 In addition to the compounds mentioned in the preparation examples, the following 3-cyano-4-phenyl-pyrroles of the general formula (I) may be mentioned individually:
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008

Verwendet man beispielsweise 3-Cyano-4-(2-fluor-3-chlorphenyl)-pyrrol und Chlorameisensäureethylester als Ausgangsstoffe, so läßt sich der Reaktionsablauf des erfindungsgemäßen Verfahrens durch das folgende Formelschema darstellen:

Figure imgb0009
If, for example, 3-cyano-4- (2-fluoro-3-chlorophenyl) pyrrole and ethyl chloroformate are used as starting materials, the course of the reaction of the process according to the invention can be represented by the following formula:
Figure imgb0009

Die zur Durchführung des erfindungsgemäßen Verfahrens als Ausgangsstoffe benötigten 1H-3-Cyano-4-phenyl-pyrrole sind durch die Formel (II) allgemein definiert. In dieser Formel (II) steht Ar vorzugsweise für diejenigen Reste, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Stoffe der Formel (I) als bevorzugt für diesen Substituenten genannt wurden.Formula (II) provides a general definition of the 1H-3-cyano-4-phenyl-pyrroles required as starting materials for carrying out the process according to the invention. In this formula (II), Ar preferably represents those Residues which have already been mentioned as preferred for this substituent in connection with the description of the substances of the formula (I) according to the invention.

Die 1H-3-Cyano-4-phenyl-pyrrole der Formel (II) sind noch nicht bekannt. Sie sind jedoch Gegenstand der eigenen vorgängigen, noch nicht publizierten deutschen Patentanmeldung P 3737984 vom 09.11.1987 und erhältlich in Analogie zu bekannten Verfahren (vgl. z.B. EP 236272, DE-OS 2927480), beispielsweise wenn manThe 1H-3-cyano-4-phenyl-pyrroles of the formula (II) are not yet known. However, they are the subject of the previous German patent application P 3737984 of November 9, 1987, which has not yet been published and is obtainable in analogy to known processes (cf. e.g. EP 236272, DE-OS 2927480), for example if one

a) Fluoraniline der Formel (IV),

Figure imgb0010
in welcher

R¹
die oben angegebene Bedeutung hat,


zunächst in einer ersten Stufe mit Acrylnitril unter üblichen Diazotierungsbedingungen, beispielsweise in Gegenwart von Natriumnitrit und Salzsäure, und in Gegenwart eines geeigneten Metallsalz-Katalysators, wie beispielsweise Kupfer-II-chlorid oder Kupfer-II-oxid, und gegebenenfalls in Gegenwart eines geeigneten Verdünnungsmittels, wie beispielsweise Aceton oder Wasser, bei Temperaturen zwischen  -20°C und  +50°C umsetzt ("Meerwein-Arylierung"; vgl. hierzu auch Organic Reactions 11, 189 [1960]; Organic Reactions 24, 225 [1976] oder C. Ferri "Reaktionen der organischen Synthese" S. 319, Thieme Verlag Stuttgart 1978) und dann in einer 2. Stufe die so erhältlichen substituierten α-Chlor-β-phenylpropionitrile der Formel (V),
Figure imgb0011
 in welcher
R¹
die oben angegebene Bedeutung hat,


mit Basen, wie beispielsweise Triethylamin oder Diazabicycloundecen, in üblicher Art und Weise gegebenenfalls in Gegenwart eines Verdünnungsmittels, wie beispielsweise Tetrahydrofuran, bei Temperaturen zwischen 0°C und 50°C dehydrohalogeniert (vgl. auch die Herstellungsbeispiele) oder alternativ, wenn mana) fluoroanilines of the formula (IV),
Figure imgb0010
 in which
R¹
has the meaning given above,


first in a first step with acrylonitrile under customary diazotization conditions, for example in the presence of sodium nitrite and hydrochloric acid, and in the presence of a suitable metal salt catalyst, such as copper (II) chloride or copper (II) oxide, and if appropriate in the presence of a suitable diluent, such as acetone or water, at temperatures between -20 ° C and + 50 ° C ("sea wine arylation"; see also Organic Reactions 11 , 189 [1960]; Organic Reactions 24 , 225 [1976] or C. Ferri "Reactions in Organic Synthesis" p. 319, Thieme Verlag Stuttgart 1978) and then in a second stage the substituted α-chloro-β-phenylpropionitriles of the formula (V) ,
Figure imgb0011
 in which
R¹
has the meaning given above,


with bases, such as, for example, triethylamine or diazabicycloundecene, in the usual manner, if appropriate in the presence of a diluent, such as, for example, tetrahydrofuran, dehydrohalogenated at temperatures between 0 ° C. and 50 ° C. (cf. also the preparation examples) or, alternatively, if

b) substituierte Benzaldehyde der Formel (VI),

Figure imgb0012
in welcher

R¹
die oben angegebene Bedeutung hat,


mit Cyanessigsäure der Formel (VII)
NC-CH₂-COOH
Figure imgb0013
in üblicher Art und Weise in Gegenwart einer Base, wie beispielsweise Piperidin oder Pyridin, und gegebenenfalls in Gegenwart eines geeigneten Verdünnungsmittels, wie beispielsweise Pyridin, bei Temperaturen zwischen 50°C und 120°C kondensiert und gleichzeitig decarboxyliert (vgl. z.B. "Organikum" S. 571/572; 15. Auflage; VEB Deutscher Verlag der Wissenschaften Berlin 1981 sowie die Herstellungsbeispiele), und die so [nach Verfahren (a) oder (b)] erhältlichen substituierten Zimtsäurenitrile der Formel (VIII),
Figure imgb0014
in welcher
R¹
die oben angegebene Bedeutung hat,


mit Sulfonylmethylisocyaniden der Formel (IX),
R³-SO₂-CH₂-NC
Figure imgb0015
in welcher
R³
für Alkyl oder für gegebenenfalls substituiertes Aryl, insbesondere für Methyl, für 4-Methylphenyl, 4-Chlorphenyl oder für Phenyl steht,


in Gegenwart einer Base wie beispielsweise Natriumhydrid und gegebenenfalls in Gegenwart eines Verdünnungsmittels wie beispielsweise Tetrahydrofuran bei Temperaturen zwischen  -20°C und  +50°C umsetzt.b) substituted benzaldehydes of the formula (VI),
Figure imgb0012
 in which
R¹
has the meaning given above,


with cyanoacetic acid of formula (VII)
NC-CH₂-COOH
Figure imgb0013
condensed in the usual manner in the presence of a base, such as, for example, piperidine or pyridine, and optionally in the presence of a suitable diluent, such as, for example, pyridine, at temperatures between 50 ° C. and 120 ° C. and decarboxylated at the same time (see, for example, “Organikum” p 571/572; 15th edition; VEB Deutscher Verlag der Wissenschaften Berlin 1981 as well as the production examples), and the substituted cinnamic acid nitriles of the formula (VIII) obtainable [by process (a) or (b)],
Figure imgb0014
in which
R¹
has the meaning given above,


with sulfonylmethyl isocyanides of the formula (IX),
R³-SO₂-CH₂-NC
Figure imgb0015
in which
R³
represents alkyl or optionally substituted aryl, in particular methyl, 4-methylphenyl, 4-chlorophenyl or phenyl,


in the presence of a base such as sodium hydride and optionally in the presence of a diluent such as tetrahydrofuran at temperatures between -20 ° C and + 50 ° C.

Fluoraniline der Formel (IV) sind teilweise bekannt (vgl. z.B. J. org. Chem. 39, 1758-1761 [1974]: J. med. Chem. 12, 195-196 [1969] oder US-PS 3900519).Fluoranilines of the formula (IV) are known in some cases (cf., for example, J. org. Chem. 39 , 1758-1761 [1974]: J. med. Chem. 12 , 195-196 [1969] or US Pat. No. 3,900,519).

Die weiterhin als Vorprodukte zur Herstellung der neuen Ausgangsprodukte der Formel (II) nach Variante b) benötigten Fluorbenzaldehyde der Formel (VI) sind größtenteils bekannt (vgl. z.B. Chem. Abstr. 100: 209 388k bzw. Jap. Pat. 58/222045), so ist der 3-Chlor-5-fluor-benzaldehyd mit Reg.-No. 90390-49-1 und der 3-Chlor-6-fluor-benzaldehyd mit Reg.-No. 96515-79-6 in Chem. Abs. registriert. Die Cyanessigsäure der Formel (VII) ist eine allgemein bekannte Verbindung der organischen Chemie.Most of the fluorobenzaldehydes of the formula (VI) required as precursors for the preparation of the new starting materials of the formula (II) according to variant b) are known (cf., for example, Chem. Abstr. 100 : 209 388k or Jap. Pat. 58/222045) , the 3-chloro-5-fluoro-benzaldehyde with Reg.-No. 90390-49-1 and the 3-chloro-6-fluoro-benzaldehyde with Reg.-No. 96515-79-6 registered in Chem. Abs. The cyanoacetic acid of the formula (VII) is a generally known compound of organic chemistry.

Die weiterhin als Vorprodukte zur Herstellung der neuen Ausgangsprodukte der Formel (II) benötigten Sulfonyl-methylisocyanide der Formel (IX) sind ebenfalls bekannt (vgl. z.B., Synthesis 1985, 400-402; Org. Syntheses 57, 102-106 [1977]; J. org. Chem. 42, 1153-1159 [1977]; Tetrahedron Lett. 1972, 2367-2368).The sulfonyl methyl isocyanides of the formula (IX) which are also required as precursors for the preparation of the new starting materials of the formula (II) are also known (cf., for example, Synthesis 1985 , 400-402; Org. Syntheses 57 , 102-106 [1977]; J. org. Chem. 42 , 1153-1159 [1977]; Tetrahedron Lett. 1972 , 2367-2368).

Die zur Durchführung des erfindungsgemäßen Verfahrens weiterhin als Ausgangsstoffe benötigten Acylierungsmittel sind durch die Formel (III) allgemein definiert. In dieser Formel (III) steht R vorzugsweise für diejenigen Reste, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Stoffe der Formel (I) als bevorzugt für diesen Substituenten genannt wurden.

E
steht vorzugsweise für Halogen, insbesondere für Chlor oder Brom, oder für einen Anhydridrest der Formel
Figure imgb0016
 wobei R die oben angegebene Bedeutung hat.

Formula (III) provides a general definition of the acylating agents which are furthermore required as starting materials for carrying out the process according to the invention. In this formula (III), R preferably represents those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.
E
preferably represents halogen, in particular chlorine or bromine, or an anhydride radical of the formula
Figure imgb0016
 where R has the meaning given above.

Die Acylierungsmittel der Formel (III) sind allgemein bekannte Verbindungen der organischen Chemie.The acylating agents of the formula (III) are generally known compounds of organic chemistry.

Alternativ zur Herstellung der Vorprodukte der Formel (II) mit Hilfe der im vorangegangenen beschriebenen Herstellungsverfahren sind verschiedene weitere Herstellungsverfahren zur Herstellung der Vorprodukte der Formel (II) denkbar.As an alternative to the production of the precursors of formula (II) with the aid of the manufacturing processes described above, various other manufacturing processes for the production of the precursors of formula (II) are conceivable.

So erhält man 1H-3-Cyano-4-phenyl-pyrrole der Formel (II) beispielsweise auch, wenn man α-Cyanozimtsäureester in Gegenwart von Basen und in Gegenwart von Kupfer- (II)-Salzen mit p-Toluol-sulfonylmethylisocyanid umsetzt (vgl. J6-1030-571 oder J6-1200-984) oder wenn man α-substituierte Zimtsäurenitrile in Gegenwart von Natriumhydrid mit Isocyanoessigsäureestern cyclisiert, die so erhältlichen Pyrrol-2-carbonsäureester mit Basen verseift und anschließend thermisch decarboxyliert (vgl. JP 59/212468) oder wenn man Phenacylaminderivate mit geeignet substituierten Acrylnitril-Derivaten umsetzt (vgl. EP 174910) oder wenn man 3-Cyano-4-phenyl-Δ²-pyrroline in Gegenwart von Kupfer-II-Salzen oder Eisen-III-salzen oxidiert (vgl. EP 183217) oder wenn man α-Cyanoacrylsäurederivate mit Isocyanoessigsäureestern in Gegenwart einer Base umsetzt und die so erhältlichen Δ²-Pyrrolin-2-carbonsäurederivate in einer 2. Stufe in Gegenwart einer Base und in Gegenwart eines Metallsalzkatalysators oxidativ decarboxyliert (vgl. Deutsche Patentanmeldung P 3718375 vom 02.06.1987).For example, 1H-3-cyano-4-phenyl-pyrroles of the formula (II) are also obtained if α-cyanocinnamic acid esters are reacted with p-toluenesulfonylmethyl isocyanide in the presence of bases and in the presence of copper (II) salts ( see J6-1030-571 or J6-1200-984) or if one α-Substituted cinnamic acid nitriles cyclized in the presence of sodium hydride with isocyanoacetic acid esters, the pyrrole-2-carboxylic acid esters thus obtained are saponified with bases and then thermally decarboxylated (see JP 59/212468) or if phenacylamine derivatives are reacted with suitably substituted acrylonitrile derivatives (see EP 174910) or if 3-cyano-4-phenyl-Δ²-pyrroline is oxidized in the presence of copper (II) salts or iron (III) salts (cf. EP 183217) or if α-cyanoacrylic acid derivatives are reacted with isocyanoacetic acid esters in the presence of a base and the Δ²-pyrroline-2-carboxylic acid derivatives obtainable in this way are oxidatively decarboxylated in a second stage in the presence of a base and in the presence of a metal salt catalyst (cf. German Patent Application P 3718375 from June 2, 1987).

Als Verdünnungsmittel zur Durchführung des erfindungsgemäßen Verfahrens kommen inerte organische Lösungsmittel infrage. Hierzu gehören insbesondere aliphatische, alicyclische oder aromatische, gegebenenfalls halogenierte Kohlenwasserstoffe, wie beispielsweise Benzin, Benzol, Toluol, Xylol, Chlorbenzol, Petrolether, Hexan, Cyclohexan, Dichlormethan, Chloroform, Tetrachlorkohlenstoff, Ether, wie Diethylether, Dioxan, Tetrahydrofuran oder Ethylenglykoldimethyl- oder -diethylether, Ketone, wie Aceton oder Butanon, Nitrile, wie Acetonitril oder Propionitril, Amide, wie Dimethylformamid, Dimethylacetamid, N-Methylformanilid, N-Methylpyrrolidon oder Hexamethylphosphorsäuretriamid, Ester, wie Essigsäureethylester oder Sulfoxide, wie Dimethylsulfoxid.Inert organic solvents are suitable as diluents for carrying out the process according to the invention. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, ketones such as acetone or butanone, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as ethyl acetate or sulfoxides such as dimethyl sulfoxide.

Das erfindungsgemäße Verfahren wird vorzugsweise in Gegenwart eines geeigneten Reaktionshilfsmittels durchgeführt. Als solche kommen alle üblichen anorganischen oder organischen Basen in Frage. Hierzu gehören beispielsweise Alkalimetallhydroxide, wie Natriumhydroxid oder Kaliumhydroxid, Alkalimetall-carbonate, wie Natriumcarbonat, Kaliumcarbonat oder Natriumhydrogencarbonat, sowie tertiäre Amine, wie Triethylamin, N,N-Dimethylanilin, Pyridin, N,N-Dimethylaminopyridin, Diazabicyclooctan (DABCO), Diazabicyclononen (DBN) oder Diazabicycloundecen (DBU).The process according to the invention is preferably carried out in the presence of a suitable reaction auxiliary. All conventional inorganic or organic bases are suitable as such. These include, for example, alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate, and also tertiary amines, such as triethylamine, N, N-dimethylaniline, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclooctane (DABCO), diazabicyclooctane (DABCO) ) or diazabicycloundecene (DBU).

Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßen Verfahrens in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen  -20°C und 150°C, vorzugsweise bei Temperaturen zwischen 0°C und 80°C.The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between -20 ° C and 150 ° C, preferably at temperatures between 0 ° C and 80 ° C.

Zur Durchführung des erfindungsgemäßen Verfahrens setzt man pro Mol an 1H-3-Cyano-4-phenyl-pyrrol der Formel (II) im allgemeinen 1.0 bis 5.0 Mol, vorzugsweise 1.0 bis 1.5 Mol an Acylierungsmittel der Formel (III) und gegebenenfalls 1.0 bis 5.0 Mol, vorzugsweise 1.0 bis 1.5 Mol an Reaktionshilfsmittel ein.To carry out the process according to the invention, 1.0 to 5.0 mol, preferably 1.0 to 1.5 mol, of acylating agent of the formula (III) and, if appropriate, 1.0 to 5.0, are generally employed per mol of 1H-3-cyano-4-phenylpyrrole of the formula (II) Mol, preferably 1.0 to 1.5 mol of reaction aids.

Die Reaktionsdurchführung, Aufarbeitung und Isolierung der Reaktionsprodukte erfolgt nach allgemein üblichen Methoden (vgl. auch die Herstellungsbeispiele).The reaction products are worked up, worked up and isolated using generally customary methods (cf. also the preparation examples).

Die erfindungsgemäßen Wirkstoffe weisen eine starke Wirkung gegen Schädlinge auf und können zur Bekämpfung von unerwünschten Schadorganismen praktisch eingesetzt werden. Die Wirkstoffe sind z.B. für den Gebrauch als Pflanzenschutzmittel insbesondere als Fungizide geeignet.The active compounds according to the invention have a strong action against pests and can be used practically to combat undesirable harmful organisms will. The active ingredients are suitable, for example, for use as crop protection agents, in particular as fungicides.

Fungizide Mittel im Pflanzenschutz werden eingesetzt zur Bekämpfung von Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Beispielhaft aber nicht begrenzend seien einige Erreger von pilzlichen Erkrankungen, die unter die oben aufgezählten Oberbegriffe fallen, genannt:
Pythium-Arten, wie beispielsweise Pythium ultimum;
Phytophthora-Arten, wie beispielsweise Phytophthora infestans;
Pseudoperonospora-Arten, wie beispielsweise Pseudoperonospora humuli oder Pseudoperonospora cubensis;
Plasmopara-Arten, wie beispielsweise Plasmopara viticola;
Peronospora-Arten, wie beispielsweise Peronospora pisi oder P. brassicae;
Erysiphe-Arten, wie beispielsweise Erysiphe graminis;
Sphaerotheca-Arten, wie beispielsweise Sphaerotheca fuliginea;
Podosphaera-Arten, wie beispielsweise Podosphaera leucotricha;
Venturia-Arten, wie beispielsweise Venturia inaequalis;
Pyrenophora-Arten, wie beispielsweise Pyrenophora teres oder P. graminea
(Konidienform: Drechslera, Syn: Helminthosporium);
Cochliobolus-Arten, wie beispielsweise Cochliobolus sativus
(Konidienform: Drechslera, Syn: Helminthosporium);
Uromyces-Arten, wie beispielsweise Uromyces appendiculatus;
Puccinia-Arten, wie beispielsweise Puccinia recondita;
Tilletia-Arten, wie beispielsweise Tilletia caries;
Ustilago-Arten, wie beispielsweise Ustilago nuda oder Ustilago avenae;
Pellicularia-Arten, wie beispielsweise Pellicularia sasakii;
Pyricularia-Arten, wie beispielsweise Pyricularia oryzae;
Fusarium-Arten, wie beispielsweise Fusarium culmorum;
Botrytis-Arten, wie beispielsweise Botrytis cinerea;
Septoria-Arten, wie beispielsweise Septoria nodorum;
Leptosphaeria-Arten, wie beispielsweise Leptosphaeria nodorum;
Cercospora-Arten, wie beispielsweise Cercospora canescens;
Alternaria-Arten, wie beispielsweise Alternaria brassicae;
Pseudocercosporella-Arten, wie beispielsweise Pseudocercosporella herpotrichoides.Some pathogens of fungal diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Pythium species, such as, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as, for example, Plasmopara viticola;
Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea
(Conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus sativus
(Conidial form: Drechslera, Syn: Helminthosporium);
Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Alternaria brassicae;
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

Die gute Pflanzenverträglichkeit der Wirkstoffe in den zur Bekämpfung von Pflanzenkrankheiten notwendigen Konzentrationen erlaubt eine Behandlung von oberirdischen Pflanzenteilen, von Pflanz- und Saatgut, und des Bodens.The fact that the active ingredients are well tolerated by plants in those necessary to combat plant diseases Concentrations allow treatment of above-ground parts of plants, plant and seed, and the soil.

Dabei lassen sich die erfindungsgemäßen Wirkstoffe mit besonders gutem Erfolg zur Bekämpfung von Krankheiten im Obst- und Gemüseanbau, wie beispielsweise gegen den Erreger des Bohnengrauschimmels (Botrytis cinerea), oder zur Bekämpfung von Reiskrankheiten, wie beispielsweise gegen den Erreger der Reisfleckenkrankheit (Pyricularia oryzae) oder zur Bekämpfung von Getreidekrankheiten, wie beispielsweise gegen den Erreger der Braunspelzigkeit des Weizens (Leptosphaeria nodorum) oder gegen den Erreger des Getreideschneeschimmels (Fusarium nivale) einsetzen. Darüberhinaus besitzen die erfindungsgemäßen Wirkstoffe eine gute fungizide in-vitro-Wirksamkeit.The active compounds according to the invention can be used with particularly good success for combating diseases in fruit and vegetable cultivation, such as, for example, against the pathogen of gray bean mold (Botrytis cinerea), or for combating rice diseases, for example against the pathogen of rice stain disease (Pyricularia oryzae) or to combat cereal diseases, such as against the pathogen causing brown fur in the wheat (Leptosphaeria nodorum) or against the pathogen causing cereal snow mold (Fusarium nivale). In addition, the active compounds according to the invention have good fungicidal activity in vitro.

Die Wirkstoffe können in Abhängigkeit von ihren jeweiligen physikalischen und/oder chemischen Eigenschaften in übliche Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Schäume, Pasten, Granulate, Aerosole, Feinstverkapselungen in polymeren Stoffen und in Hüllmassen für Saatgut, sowie ULV-Kalt- und Warmnebel-Formulierungen.Depending on their respective physical and / or chemical properties, the active ingredients can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV Cold and warm fog formulations.

Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Ether und Ester, Ketone, wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z.B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlendioxid; als feste Trägerstoffe kommen in Frage: z.B. natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als feste Trägerstoffe für Granulate kommen in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengel; als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäure-Ester, Polyoxyethylen-Fettalkohol-Ether, z.B. Alkylarylpolyglykol-Ether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose.These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, under pressure standing liquefied gases and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; Solid carrier materials are suitable: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stems; suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; The following may be used as dispersants: for example lignin sulfite waste liquor and methyl cellulose.

Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine, und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein.Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalocyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90%.The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

Die erfindungsgemäßen Wirkstoffe können in den Formulierungen in Mischung mit anderen bekannten Wirkstoffen vorliegen wie Fungizide, Insektizide, Akarizide und Herbizide sowie in Mischungen mit Düngemitteln und Wachstumsregulatoren.The active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and in mixtures with fertilizers and growth regulators.

Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus bereiteten Anwendungsformen wie gebrauchsfertige Lösungen, Suspensionen, Spritzpulver, Pasten, lösliche Pulver, Stäubemittel und Granulate angewendet werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Verspritzen, Versprühen, Verstreuen, Verstäuben, Verschäumen, Bestreichen usw.. Es ist ferner möglich, die Wirkstoffe nach dem Ultra-Low-Volume-Verfahren auszubringen oder die Wirkstoffzubereitung oder den Wirkstoff selbst in den Boden zu injizieren. Es kann auch das Saatgut der Pflanzen behandelt werden.The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.

Bei der Behandlung von Pflanzenteilen können die Wirkstoffkonzentrationen in den Anwendungsformen in einem größeren Bereich variiert werden. Sie liegen im allgemeinen zwischen 1 und 0,0001 Gew.-%, vorzugsweise zwischen 0,5 und 0,001%.When treating parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

Bei der Saatgutbehandlung werden im allgemeinen Wirkstoffmengen von 0,001 bis 50 g je Kilogramm Saatgut, vorzugsweise 0,01 bis 10 g benötigt.In the case of seed treatment, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

Bei Behandlung des Bodens sind Wirkstoffkonzentrationen von 0,00001 bis 0,1 Gew.-%, vorzugsweise von 0,0001 bis 0,02% am Wirkungsort erforderlich.When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.

HerstellungsbeispieleManufacturing examples Beispiel 1example 1

Figure imgb0017
Figure imgb0017

Zu 3,0 g (0.136 Mol) 3-Cyano-4-(2-fluor-3-chlorphenyl)-pyrrol in einer Mischung aus 120 ml Dichlormethan/ Tetrahydrofuran (5: 1) gibt man 1,46 g (0.0143 Mol) Acetanhydrid, 1,45 g (0.0143 Mol) Triethylamin und 0,2 g 4-Dimethylaminopyridin, rührt 16 Stunden bei Raumtemperatur, wäscht zweimal mit Wasser, trocknet über Natriumsulfat und engt im Vakuum ein.1.46 g (0.0143 mol) are added to 3.0 g (0.136 mol) of 3-cyano-4- (2-fluoro-3-chlorophenyl) pyrrole in a mixture of 120 ml of dichloromethane / tetrahydrofuran (5: 1). Acetic anhydride, 1.45 g (0.0143 mol) of triethylamine and 0.2 g of 4-dimethylaminopyridine, stirred for 16 hours at room temperature, washed twice with water, dried over sodium sulfate and concentrated in vacuo.

Man erhält 2,4 g (67,2% der Theorie) an 1-Acetyl-3-cyano-4-(2-fluor-3-chlorphenyl)-pyrrol vom Schmelzpunkt 141°C-142°C.2.4 g (67.2% of theory) of 1-acetyl-3-cyano-4- (2-fluoro-3-chlorophenyl) pyrrole, melting point 141 ° C.-142 ° C., are obtained.

Beispiel 2Example 2

Figure imgb0018
Figure imgb0018

Zu 0,65 g (0.022 Mol) Natriumhydrid (80 prozentig in Paraffinöl) in 20 ml Dimethoxyethan gibt man bei Raumtemperatur tropfenweise unter Rühren 4,0 g (0.0182 Mol) 3-Cyano-4-(2-fluor-3-chlorphenyl)-pyrrol in 60 ml Dimethoxyethan und rührt anschließend zwei weitere Stunden bei Raumtemperatur. Danach gibt man ebenfalls bei Raumtemperatur tropfenweise unter Rühren 3,4 g (0.032 Mol) Chlorameisensäureethylester in 20 ml Dimethoxyethan gelöst zu, rührt weitere 3 Stunden bei Raumtemperatur, hydrolysiert mit Wasser, extrahiert mit Essigester, wäscht zweimal mit Wasser, trocknet über Natriumsulfat und entfernt das Lösungsmittel im Vakuum.4.0 g (0.0182 mol) of 3-cyano-4- (2-fluoro-3-chlorophenyl) are added dropwise at room temperature to 0.65 g (0.022 mol) of sodium hydride (80 percent in paraffin oil) in 20 ml of dimethoxyethane with stirring. pyrrole in 60 ml of dimethoxyethane and then stirred for two more hours at room temperature. Thereafter, 3.4 g (0.032 mol) of ethyl chloroformate dissolved in 20 ml of dimethoxyethane are also added dropwise with stirring at room temperature, the mixture is stirred for a further 3 hours at room temperature, hydrolyzed with water, extracted with ethyl acetate, washed twice with water, dried over sodium sulfate and removed the solvent in vacuo.

Man erhält 4,9 g (92% der Theorie) an 1-Ethoxycarbonyl-3-cyano-4-(2-fluor-3-chlorphenyl)-pyrrol vom Schmelzpunkt 149°C.4.9 g (92% of theory) of 1-ethoxycarbonyl-3-cyano-4- (2-fluoro-3-chlorophenyl) pyrrole with a melting point of 149 ° C. are obtained.

Herstellung der AusgangsverbindungPreparation of the starting compound Beispiel II-1Example II-1

Figure imgb0019
Figure imgb0019

Zu 1,4 g (0.0464 Mol) Natriumydrid (80 %ig in Mineralöl) in 17,5 ml Tetrahydrofuran unter einer Argonschutzgasatmosphäre gibt man bei  -10°C bis  -20°C tropfenweise unter Rühren eine Lösung von 6,0 g (0.0331 Mol) 3-(2-Fluor-3-chlorphenyl)-acrylnitril und 7,8 g (0.0431 Mol) p-Toluolsulfonylmethylisocyanid in 20 ml einer Mischung aus Tetrahydrofuran/Dimethylsulfoxid (5: 1). Nach beendeter Zugabe läßt man die Reaktionsmischung auf Raumtemperatur kommen, gibt Wasser zu, extrahiert mehrfach mit Essigester, wäscht die vereinigten Essigesterphasen mit Wasser, trocknet über Natriumsulfat und engt im Vakuum ein. Der Rückstand wird durch Chromatographie an Kieselgel (Laufmittel: Cyclohexan/Essigester 5: 1) gereinigt.To 1.4 g (0.0464 mol) of sodium hydride (80% in mineral oil) in 17.5 ml of tetrahydrofuran under an argon protective gas atmosphere, a solution of 6.0 g (0.0331 Mol) of 3- (2-fluoro-3-chlorophenyl) acrylonitrile and 7.8 g (0.0431 mol) of p-toluenesulfonylmethyl isocyanide in 20 ml of a mixture of tetrahydrofuran / dimethyl sulfoxide (5: 1). When the addition is complete, the reaction mixture is allowed to come to room temperature, water is added, the mixture is extracted several times with ethyl acetate, the combined ethyl acetate phases are washed with water, dried over sodium sulfate and concentrated in vacuo. The residue is purified by chromatography on silica gel (mobile phase: cyclohexane / ethyl acetate 5: 1).

Man erhält 3,3 g (45% der Theorie) an 3-Cyano-4-(2-fluor-3-chlorphenyl)-pyrrol vom Schmelzpunkt 180°C-181°C.3.3 g (45% of theory) of 3-cyano-4- (2-fluoro-3-chlorophenyl) pyrrole with a melting point of 180 ° C.-181 ° C. are obtained.

Beispiel VIII-1Example VIII-1

Figure imgb0020
Figure imgb0020

Zu einer Lösung aus 40,1 g (0.25 Mol) 2-Fluor-3-chlorbenzaldehyd (vgl. z.B. DE 3129274) in 170 ml Pyridin gibt man 2,5 ml Piperidin und 22,9 g (0.27 Mol) Cyanessigsäure und erhitzt 14 Stunden auf Rückflußtemperatur. Zur Aufarbeitung engt man im Vakuum ein, nimmt den Rückstand in Essigester auf, wäscht nacheinander mit 1 normaler Salzsäure, mit wässriger Natriumhydrogensulfitlösung sowie mit Wasser, trocknet über Natriumsulfat und engt im Vakuum ein. Das verbleibende Öl läßt sich durch Chromtographie an Kieselgel (Laufmittel: Cyclohexan Essigester 5: 1) reinigen.2.5 ml of piperidine and 22.9 g (0.27 mol) of cyanoacetic acid are added to a solution of 40.1 g (0.25 mol) of 2-fluoro-3-chlorobenzaldehyde (see, for example, DE 3129274) in 170 ml of pyridine, and the mixture is heated 14 Hours at reflux temperature. For working up, the mixture is concentrated in vacuo, the residue is taken up in ethyl acetate, washed successively with 1 normal hydrochloric acid, with aqueous sodium bisulfite solution and with water, dried over sodium sulfate and concentrated in vacuo. The remaining oil can be purified by chromatography on silica gel (mobile phase: cyclohexane ethyl acetate 5: 1).

Man erhält 16,9 g (37% der Theorie) an 3-(2-Fluor-3-chlorphenyl)-acrylnitril vom Schmelzpunkt 90°C-92°C.16.9 g (37% of theory) of 3- (2-fluoro-3-chlorophenyl) acrylonitrile with a melting point of 90 ° C.-92 ° C. are obtained.

In entsprechender Weise und gemäß den allgemeinen Angaben zur Herstellung erhält man die folgenden 3-Cyano-4-phenyl-pyrrol-Derivate der allgemeinen Formel (I):

Figure imgb0021
The following 3-cyano-4-phenyl-pyrrole derivatives of the general formula (I) are obtained in a corresponding manner and in accordance with the general information on the preparation:
Figure imgb0021

AnwendungsbeispieleExamples of use

In den folgenden Anwendungsbeispielen wurden die nachstehend aufgeführten Verbindungen als Vergleichsubstanzen eingesetzt;

Figure imgb0022
In the following application examples, the compounds listed below were used as comparison substances;
Figure imgb0022

3-Cyano-4-(2,3-dichlorphenyl)-pyrrol (vgl. EP 174910 sowie EP 236272)
und/oder

Figure imgb0023
3-cyano-4- (2,3-dichlorophenyl) pyrrole (see EP 174910 and EP 236272)
and or
Figure imgb0023

1-Acetyl-3-cyano-4-(2,3-dichlorphenyl)-pyrrol (vgl. DE-OS 2927480)
und/oder

Figure imgb0024
1-acetyl-3-cyano-4- (2,3-dichlorophenyl) pyrrole (see DE-OS 2927480)
and or
Figure imgb0024

1-Methoxyacetyl-3-cyano-4-(2,3-dichlorphenyl)-pyrrol (vgl. Jp. Kokai Tokkyo Koho 81-79672).1-methoxyacetyl-3-cyano-4- (2,3-dichlorophenyl) pyrrole (see Jp. Kokai Tokkyo Koho 81-79672).

Beispiel AExample A

Botrytis-Test (Bohne)/protektiv

Lösungsmittel:
4,7 Gewichtsteile Aceton
Emulgator:
D,3 Gewichtsteile Alkylarylpolyglykolether

Botrytis test (bean) / protective
Solvent:
4.7 parts by weight of acetone
Emulsifier:
D, 3 parts by weight of alkylaryl polyglycol ether

Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt daß Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

Zur Prüfung auf protektive Wirksamkeit bespritzt man junge Pflanzen mit der Wirkstoffzubereitung bis zur Tropfnässe. Nach Antrocknen des Spritzbelages werden auf jedes Blatt 2 kleine mit Botrytis cinerea bewachsene Agarstückchen aufgelegt. Die inokulierten Pflanzen werden in einer abgedunkelten, feuchten Kammer bei 20°C aufgestellt. 3 Tage nach der Inokulation wird die Größe der Befallsflecken auf den Blättern ausgewertet.To test for protective efficacy, young plants are sprayed with the active compound preparation to runoff. After the spray coating has dried on, 2 small pieces of agar covered with botrytis cinerea are placed on each leaf. The inoculated plants are placed in a darkened, moist chamber at 20 ° C. 3 days after the inoculation, the size of the infection spots on the leaves is evaluated.

Eine deutliche Überlegenheit in der Wirksamkeit gegenüber dem Stand der Technik zeigen in diesem Test z.B. die Verbindungen gemäß den Herstellungsbeispielen: 1 und 3.In this test, for example, the compounds according to the preparation examples: 1 and 3 show a clear superiority in effectiveness compared to the prior art.

Beispiel BExample B

Pyrenophora teres-Test (Gerste)/protektiv

Lösungsmittel:
100 Gewichtsteile Dimethylformamid
Emulgator:
0,25 Gewichtsteile Alkylarylpolyglykolether

Pyrenophora teres test (barley) / protective
Solvent:
100 parts by weight of dimethylformamide
Emulsifier:
0.25 parts by weight of alkylaryl polyglycol ether

Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

Zur Prüfung auf protektive Wirksamkeit besprüht man junge Pflanzen mit der Wirkstoffzubereitung taufeucht. Nach Abtrocknen des Spritzbelages werden die Pflanzen mit einer Konidiensuspension von Pyrenophora teres besprüht. Die Pflanzen verbleiben 48 Stunden bei 20°C und 100% relativer Luftfeuchtigkeit in einer Inkubationskabine.To test for protective efficacy, young plants are sprayed with the preparation of active compound as dewy. After the spray coating has dried, the plants are sprayed with a conidia suspension of Pyrenophora teres. The plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 48 hours.

Die Pflanzen werden in einem Gewächshaus bei einer Temperatur von ca. 20°C und einer relativen Luftfeuchtigkeit von ca. 80% aufgestellt.The plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80%.

7 Tage nach der Inokulation erfolgt die Auswertung.Evaluation is carried out 7 days after the inoculation.

Eine deutliche Überlegenheit in der Wirksamkeit gegenüber dem Stand der Technik zeigen bei diesem Test z.B. die Verbindungen gemäß den Herstellungsbeispielen: 1 und 3.This test shows a clear superiority in effectiveness compared to the prior art, e.g. the compounds according to the preparation examples: 1 and 3.

Claims (8)

1. 3-Cyano-4-phenyl-pyrroles of the general formula (I)
Figure imgb0029
 in which
R¹   represents chlorine and
R²   represents in each case straight-chain or branched alkyl, alkoxy or alkoxyalkyl, each having 1 to 6 carbon atoms in the individual alkyl moieties.

2. 3-Cyano-4-phenyl-pyrroles according to Claim 1, where in the formula (I)
R¹   represents chlorine and
R²   represents in each case straight-chain or branched alkyl, alkoxy or alkoxyalkyl, each having 1 to 4 carbon atoms in the individual alkyl moieties.

3. 3-Cyano-4-phenyl-pyrroles according to Claim 1, where in the formula (I)
R¹   represents chlorine and
R²   represents methyl, ethyl, methoxy, ethoxy, methoxymethyl or ethoxymethyl.

4. Process for the preparation of 3-cyano-4-phenyl-pyrroles of the general formula (I)
Figure imgb0030
 in which
R¹   represents chlorine and
R²   represents in each case straight-chain or branched alkyl, alkoxy or alkoxyalkyl, each having 1 to 6 carbon atoms in the individual alkyl moieties, characterised in that 1H-3-cyano-4-phenyl-pyrroles of the formula (II)
Figure imgb0031
 in which
R¹   has the abovementioned meaning

are reacted with acylating agents of the formula (III)
Figure imgb0032
 in which
R²   has the abovementioned meaning and
E   represents an electron-attracting leaving group, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.

5. Pesticides, characterised in that they contain at least one 3-cyano-4-phenyl-pyrrole of the formula (I) according to Claims 1 and 4.
6. Use of 3-cyano-4-phenyl-pyrroles of the formula (I) according to Claims 1 and 4 for combating pests.
7. Method of combating pests, characterised in that 3-cyano-4-phenyl-pyrroles of the formula (I) according to Claims 1 and 4 are allowed to act on pests and/or their environment.
8. Process for the preparation of pesticides, characterised in that 3-cyano-4-phenyl-pyrroles of the formula (I) according to Claims 1 and 4 are mixed with extenders and/or surface-active agents.
EP89106817A 1988-04-29 1989-04-17 3-cyano-4-phenyl-pyrroles Expired - Lifetime EP0339417B1 (en)

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DE3814478A DE3814478A1 (en) 1988-04-29 1988-04-29 3-CYANO-4-PHENYL PYRROLE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN PEST CONTROL
DE3814478 1988-04-29

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EP0130149A1 (en) * 1983-06-17 1985-01-02 Ciba-Geigy Ag 3-Phenyl-4-cyanopyrrole derivatives, process for their preparation and their use as microbicides
EP0174910A2 (en) * 1984-09-12 1986-03-19 Ciba-Geigy Ag Process for the preparation of 4-phenyl-pyrrole derivatives

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JPS5511524A (en) * 1978-07-10 1980-01-26 Nippon Soda Co Ltd Cyanopyrrole derivative, its preparation and agricultural and horticultural fungicide
EP0236272B1 (en) * 1986-03-04 1991-06-12 Ciba-Geigy Ag Fungicidal use of a cyanopyrrole derivative

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0130149A1 (en) * 1983-06-17 1985-01-02 Ciba-Geigy Ag 3-Phenyl-4-cyanopyrrole derivatives, process for their preparation and their use as microbicides
EP0174910A2 (en) * 1984-09-12 1986-03-19 Ciba-Geigy Ag Process for the preparation of 4-phenyl-pyrrole derivatives

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CA 95 No.21 S. 637 (187069f) *

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